Small Polaron-Induced Ultrafast Ferroelectric Restoration in <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>BiFeO</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></

In this report, we apply a suite of ultrafast spectroscopic techniques and advanced calculations to reveal the interplay between electronic and lattice degrees of freedom in ferroelectric <a:math xmlns:a="http://www.w3.org/1998/Math/MathML" display="inline"><a:mrow><a:msub><a:mrow><a:mi>BiFeO</a:mi></a:mrow><a:mrow><a:mn>3</a:mn></a:mrow></a:msub></a:mrow></a:math>. Using transient sum frequency generation spectroscopy, which is sensitive to electronic polarizations, we observe a transient electronic dipole reduction upon optical excitation which recovers at 0.5 and 10 ps timescale. The time-dependent density functional theory calculation reveals that both ligand-metal charge transfer and local excitation transition occurred upon photo excitation. To reveal the nature of electronic dipole restoration, we employ transient extreme ultraviolet (EUV) spectroscopy—an element-specific ultrafast technique that follows charge dynamics of Bi, Fe, and O altogether. The transient EUV dynamics observed both ultrafast free charge carrier relaxation to excitons, as well as polaron formation. However, a timescale comparison suggests that only the polaron formation is responsible for the 0.5 ps electronic dipole restoration, whereas the faster electronic relaxation does not contribute to the ferroelectric property changes. Multireference configuration interaction calculation further corroborates this result by showing both Fe and Bi atoms shift from the ground state equilibrium—leading to the polaron formation. Our result disentangles the multidegrees of freedom in ultrafast ferroelectric modulation and identifies the pivotal motion—a local polaron formation—for the fast ferroelectric recovery. It provides crucial insights on the specific lattice distortion that could modulate properties or phase transitions of condensed matter materials.